Azo dyestuffs



Patented Aug. 22, 1939 UNITED STATES AZO DYESTUFFS Walter Kern, Sissach,and Richard Tobler,

Riehen, Switzerland,

Society of Chemical Switzerland assignors to the firm of Industry inBasle, Basel,

No Drawing. Application May 21, 1938, Serial 6 Claims.

It has been found that valuable azo-dyestuffs of the general formulawherein R1 is an aryl radical and R2 a pyrene radical, may be obtainedby uniting diazo compounds with ortho-hydroxycarboxylic acid arylides ofthe general formula wherein R2 stands for a pyrene radical.

Ortho-hydroxycarboxylic acid arylides of the above general formula mayfor example be obtained by conversion of 2:3-hydroxynaphthoic acid whichmay be substituted in the heteronucleus for example by halogen or alkoxygroups, or its functional derivatives, such as for instance the halideswith aminopyrenes, such as for instance B-aminopyrene or l-aminopyrene,as well as the nuclear substitution products thereof which may containfor instance halogen, such as chlorine or bromine, alkoxy groups, suchas methoxy .or ethoxy groups, or nitro groups as substituents.

The union of the diazo-compounds with the ortho-hydroxycarboxylic acidarylides to azo dyestuffs may be effected in usual manner in substanceor on the fiber, such as for instance on the vegetable fiber. Thediazo-compounds may for instance belong to the benzene or to thenaphthalene series. They may be obtained by diazotizing aminobenzenes oraminonaphtha- These amines may contain the most In Switzerland June 2,1937 amino-azo-benzenes.

eTENT "OFFIQE The diazo-compounds may also be used as stabilizeddiam-compounds or in the form of their N-nitros-amines or theirdiazo-aminocompounds, as well as in mixture with the arylides or theiralkali salts, respectively, in the form of preparations.

The azo-dyestuifs produced in substance may be used for dyeing orcoloring the most various materials, such as. for exampl varnishes.

lakes and The azo-dyestufi's produced according to the present inventiondye in the most various shades, and these are very fast, particularlyalso excellently fast to light; Especially valuable are the dyestuffswhich are produced on the fiber according to the usual methods of dyeingwith ice colors.

The following examples illustrate the invention, the parts being by,weight unless otherwise stated, and the parts by weight being related tothe parts by volume as in the kilo to the litre Example 1 16.2 parts of2 z5-dichloraniline re diazotized in the usual manner. Theclearsolution.thus obtained is introduced into a solution consisting of 38.7 parts ofthe conversion product from 1 mol 2:3-hydroxynaphthoic acid with 1 mol3-aminopyrene, 60 parts of sodium hydroxide solution. of 30 per centstrength, 15 parts of sodium carbonate and 2000 parts of water.

ll 00 t dyestuif thus obtained of the formula The The red-brownprecipitate Example 2 Cotton yarn is impregnated with the followinggrounding solution: 1 gram of the product of thereaction of2:3-hydroxynaphthoic acid with 3- aminopyrene is dissolved by means of 3grams of sulfite cellulose waste liquor, 5 cc. of alcohol, 3.5 cc. ofsodium hydroxide solution of 36 B. and 4 cc. of Turkey red oil, and thewhole is introduced at room temperature into a solution consisting of980 cc. of water, 10 cc. of sodium hydroxide solution of 36 per centstrength and 10 cc. of Turkey red oil, while stirring. A clear solutionis thus obtained. The material is then wrung out and developed with adiazo-solution neutralized with sodium acetate and corresponding with 2parts of 1-amino-2-methoxy-5-ch1orobenzene per 1000 parts by volume,whereupon the dyestuff of the formula is formed. There is obtained apure Bordeaux red shade of very good properties of fastness.

The following table shows a number of other shades obtainable inaccordance with the invention:

Such arylides can also be used for dyeing in the piece or for printing.

The amines which are on the basis of the diazo-compounds used in theabove table have the following formulas:

IIIH: IIIHa NO: (2) G1 01 e t e) Uocm (4) 0CH: N02

IITH: ITTH: 5 O 6 0-011:

NOz

ITIH: III-H2 7 0113 (a 0-0113 No, 01

IITHz IIIHQ OCH:

Diem-component Coupling-component Shade 1 Ortho-nittaniline Product ofthe reaction of 2:3-hydroxynaptl1oic acid Red-brown.

and 3-aminopyrene 2 2:5-d1ch1oramlme do Do. 3l-aminor2-methoxy-5-nittobenzene Bordeaux 4l-armno-Z-methoxyA-nitrobenzene Violet. 5 Meta-chloranilineYellow-brown. 6 1-am1no-2-methyl-fi-nitrobenzene. Red-brown. 7l-amino-2-methyl-4-nitrobenzene C orinth. 81-amin0-2-methyl-4-chlorobenzene Brown-red. 9 Ortho-aminoazobenzeneCorinth. 10 i-(g methyl) -phenoxy-acetylamino-2:5-dimetl1oxy-1-amino-Violet.

enzene. 11 Mg methyl) -phenoxy-acetylamino-2:5-dietl10xy-1-amino-Navy-blue.

enzene. 12 4-b(2-methy1) -phenoxy-acetylamino-2:5-diethoxy-1'amino- Do.

enzene. 13 4-1;)mino 2:5-diethoxy-2-methylsulfamide-4' nitro-l:1-azo-Black.

enzene. 14 4-amin0 2:fi-diethoxy-2'-methysulfone-4-nitro-1zl-azoben- Do.

zone. 15 4-amino 2:5-diethoxy 2'-nitro-4-methylsulfone-1:1-azoben- D0.

zone. 16 4-amino-2-methoxy fi-acetylamino-2-methylsu1fone4-nitro- Do.

1:1-azobenzene.

radical selected from the group consisting of 2 QOHHH s e s o w mmo(X11115 SIO NH.CH;

1 HQ $0M CgHl IIIO: Q agar...

Cal-I5 OOH: SOQOHI (16) H=N N=N NO:

wherein R1 is an aryl radical and R2 is an aryl radical selected fromthe group consisting of yrene and nitropyrene.

2. The azo-dyestuffs of the general formula wherein R1 is a phenylradical and. R2 is an aryl p-yrene and nitropyrene.

3. The azo -dyestufis of the general formula wherein R1 is a phenylradical.

4. The azo -dyestuff of the formula I /N=NQNHO mom-moon,

5. The azo-dyestutf of the formula 6. The azo-dyestufi of the formulaWALTER KERN.

RICHARD TOBLER.

